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Pyrite with bubble-like growths
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Pete Richards
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PostPosted: Dec 31, 2020 15:56    Post subject: Pyrite with bubble-like growths  

For years I have been puzzling over some pyrite crystals found in two quarries in Ohio. They have sharp but unusual morphologies involving major trapezohedral and diploidal faces, but most curious is that rarely there are what look like little drops of water on the faces. These drops are composed of pyrite, and we have determined that it is crystallographically continuous with the surrounding crystal. A few even have little crystal faces on top of the bubble. A few look like a little pyrite circle where the bubble burst, leaving just the rim. Sometimes one of these features occurs at the boundary between two or more crystals, and it forms a saddle shape bridging them, just as water might.

If anyone wants to explain these, that's great, but I have a simpler goal in mind here. Has anyone seen anything like this elsewhere? On pyrite or on any other mineral? Features that look like bubbles, made of the same mineral as they are growing on.



Pyrite bubble 1369a-a1.jpg
 Mineral: Pyrite
 Locality:
Suever Quarry, Delphos, Allen and Van Wert Counties, Ohio, USA
 Dimensions: crystals are several millimeters, bubbles 0.1 mm or less
 Description:
 Viewed:  5087 Time(s)

Pyrite bubble 1369a-a1.jpg



Pyrite bubble 1369a-b1.JPG
 Mineral: Pyrite
 Locality:
Suever Quarry, Delphos, Allen and Van Wert Counties, Ohio, USA
 Dimensions: crystals are several millimeters, bubbles 0.1 mm or less
 Description:
 Viewed:  5079 Time(s)

Pyrite bubble 1369a-b1.JPG



Pyrite bubble 1369a-f3.JPG
 Mineral: Pyrite
 Locality:
Suever Quarry, Delphos, Allen and Van Wert Counties, Ohio, USA
 Dimensions: crystals are several millimeters, bubbles 0.1 mm or less
 Description:
 Viewed:  5079 Time(s)

Pyrite bubble 1369a-f3.JPG



Pyrite bubble 1369b-c1.JPG
 Mineral: Pyrite
 Locality:
Suever Quarry, Delphos, Allen and Van Wert Counties, Ohio, USA
 Description:
"Wet" boundary between two crystallographically unrelated crystals.
 Viewed:  5084 Time(s)

Pyrite bubble 1369b-c1.JPG



Pyrite bubble 1369b-f1.JPG
 Mineral: Pyrite
 Locality:
Suever Quarry, Delphos, Allen and Van Wert Counties, Ohio, USA
 Dimensions: crystals are several millimeters, bubbles 0.1 mm or less
 Description:
A ring and a smaller bubble
 Viewed:  5079 Time(s)

Pyrite bubble 1369b-f1.JPG



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PostPosted: Dec 31, 2020 19:39    Post subject: Re: Pyrite with bubble-like growths  

Pete...here are two pyrrhotites from Santa Eulalia which show something similar. I think I have a galena from Naica that has one too

Happy New Year!!



thumbnail_20201231_172659.jpg
 Mineral: Pyrrhotite
 Locality:
Potosí Mine, level 10, Santo Domingo (Francisco Portillo), Santa Eulalia District, Municipio Aquiles Serdán, Chihuahua, Mexico
 Dimensions: 5cm across pyrrhotite
 Description:
Peter Megaw specimen and image
 Viewed:  5024 Time(s)

thumbnail_20201231_172659.jpg



thumbnail_20201231_172721.jpg
 Mineral: Pyrrhotite
 Locality:
Potosí Mine, level 10, Santo Domingo (Francisco Portillo), Santa Eulalia District, Municipio Aquiles Serdán, Chihuahua, Mexico
 Dimensions: 5cm across pyrrhotite
 Description:
shallower bubbles

Peter Megaw specimen and image
 Viewed:  5026 Time(s)

thumbnail_20201231_172721.jpg



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Philippe Durand




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PostPosted: Jan 01, 2021 06:21    Post subject: Re: Pyrite with bubble-like growths  

I am not a crystallographer or scientist in this mater
so be kind if my suggestions are totally wrong :)

Could it be a non-crystallographic structure (I mean amorphous) growing on a crystallographic base ?
Or a growth of pyrite around an impurity, like a pearl in an oyster ?

Or a very fast cooling of a liquid phase at the end of crystallization ?

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PostPosted: Jan 01, 2021 08:40    Post subject: Re: Pyrite with bubble-like growths  

Hello Pete, all,
I am thinking of late crystallization (like parallel growth type).
The freshly crystallized micro-pyrite at this time would have been in competition with a dissolution phenomenon.
In this case, at the end of the crystallization process, the kinetics of dissolution favor the disappearance of edges and corners, thus producing a globular shape.
In any case the question is very relevant and deserves reflection.

In Ukrainian beryls, dissolution causes negative cavities.
What do you think ?
Roger.
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PostPosted: Jan 01, 2021 12:06    Post subject: Re: Pyrite with bubble-like growths  

Thanks for suggestions. Extra ideas are always welcome.

Philippe, your ideas are good ones, but I don't think they apply in this case. We studied these crystals and found that the bubbles are part of the same single crystal. This finding proves that they are not amorphous, or crystallized in layers like a pearl, a rapidly cooled liquid. Any of these would either contain many crystals in different orientations (or no crystals at all, in the case of amorphous materials), but this is not what the x-ray studies showed.

Roger, dissolution at the end of growth or after the growth period definitely attacks edges and corners first, as well as defects and cracks in the main body of the crystal. But the edges of these crystals are perfectly sharp with no rounding. Only the bubbles are rounded. And they generally have a reversed curvature where they meet the main crystal, which would be harder to explain as a result of dissolution. I attach a sketch of the cross-section of what I think of as the typical bubble.

Thanks again for thinking about these curious misbehaving crystals!



BUBBLE.jpeg
 Description:
Schematic cross section of a "typical" bubble.
 Viewed:  4877 Time(s)

BUBBLE.jpeg



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PostPosted: Jan 01, 2021 13:07    Post subject: Re: Pyrite with bubble-like growths  

Pete, another idea:

Could you have deep inside the crystal a default in the crystal lattice (an inclusion of something) which is locally deforming the crystal; and your bubble is just the outside outcome of the phenomenon ?

like an object under the carpet :)

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PostPosted: Jan 01, 2021 13:37    Post subject: Re: Pyrite with bubble-like growths  

This phenomenon is not limited to metallic minerals; I saw the same type of perfectly smooth (to the naked eye) dome on the surface of a Herkimer quartz once. I cannot speculate about a cause - No idea at all.
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PostPosted: Jan 01, 2021 15:15    Post subject: Re: Pyrite with bubble-like growths  

I think this is not a problem. I see in this crystal a big difference in the time scale.
I therefore suppose that "long" after the first perfect crystallization and a long resting time, the initial crystal underwent a last micro supply of pyrite in parallel growth in a new supply of FeS2, under uncertain equilibrium conditions, since the redissolution was able to do its work, without resetting an attack on the edges of the large crystal already stabilized. Because it was a superficial mini-episode.
In any crystallization, crystal growth is the result of two reactions in opposite directions:
1) material deposit, 2) material removal. It is for this reason that the thermodynamically most stable sites are the seat of regular growth.
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PostPosted: Jan 03, 2021 01:54    Post subject: Re: Pyrite with bubble-like growths  

I always thought that this was a subsurface oxidation process going on, pushing up some of the material above it.


299C.jpg
 Mineral: Galena on Fluorite
 Locality:
West Pastures Mine, Stanhope, Weardale, North Pennines Orefield, County Durham, England / United Kingdom
 Dimensions: 10mm x 10mm x 5 mm
 Description:
 Viewed:  4726 Time(s)

299C.jpg


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PostPosted: Jan 03, 2021 06:06    Post subject: Re: Pyrite with bubble-like growths  

This may not be the same phenomenon but viewers may find it interesting just the same. The termination of a fluorapatite crystal from Panasqueira, Portugal. 4 cm across.


Fluorapatite - Portugal SC-336 25-10-6.JPG
 Mineral: Fluorapatite
 Locality:
Minas da Panasqueira, Aldeia de São Francisco de Assis, Covilhã, Castelo Branco, Cova da Beira, Centro, Portugal
 Dimensions: 4 cm
 Description:
 Viewed:  4686 Time(s)

Fluorapatite - Portugal SC-336 25-10-6.JPG



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PostPosted: Jan 05, 2021 22:03    Post subject: Re: Pyrite with bubble-like growths  

Pete,
Thank you for posting this fun puzzle for us to think about over the holidays.

1) I own many spherical pyrite concretions formed in a limestone environment, nucleating on organic matter. Is there any way that these bumps could have formed from iron rich clay which later filled a cavity?

2) These bumps might be due to a complex series of events:
a) Outer surface of pyrite oxidizes to a thin layer of hematite.
b) Pinholes and popped bubble residue are formed in some locations.
c) Later source of iron and sulfide ions preferentially deposit epitaxially at a rapid rate at locations of b)

I am not happy with either of these explanations, so I hope you receive more suggestions.

-Dean
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PostPosted: Jan 06, 2021 08:06    Post subject: Re: Pyrite with bubble-like growths  

Hi, Pete. How are you?

As a pyrite fan, I'm curious to know your explanation.
"Very naively" I assume a melting that affected only the sub-millimeter (autotactic?) crystals, where the degree or duration of temperature could easier work. This could also explain the occasional residual facets (when the melting was not complete).
However, I don't understand the role of crystallographic continuity which you have certainly specified for a valid reason.

Just for fun, I attach a pyrite from Niccioleta mine where the feature is "only apparently" similar to your specimen.
In fact, although the drops are the same mineral (melnikovite FeS2) of the underlying pyrite, being amorphous they cannot be in a crystallographic continuity with it.

A very warm greeting.
Sante



IMG_20210106_115049.jpg
 Mineral: Pyrite, melnikovite
 Locality:
Niccioleta Mine, Massa Marittima, Grosseto Province, Tuscany, Italy
 Dimensions: 71 x 57 mm
 Description:
 Viewed:  4481 Time(s)

IMG_20210106_115049.jpg



IMG_20210106_114949.jpg
 Mineral: Pyrite, melnikovite
 Locality:
Niccioleta Mine, Massa Marittima, Grosseto Province, Tuscany, Italy
 Dimensions: 71 x 57 mm
 Description:
 Viewed:  4475 Time(s)

IMG_20210106_114949.jpg


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PostPosted: Jan 06, 2021 16:16    Post subject: Re: Pyrite with bubble-like growths  

I thought that pyrite won't melt, upon heating it will decompose to Iron and Sulphur at a certain temperature.
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PostPosted: Jan 06, 2021 19:58    Post subject: Re: Pyrite with bubble-like growths  

Could some of these structures be spiral growth hillocks with rounded edges? Such tend to develop on small cracks or irregular boundaries on the underlying surface.
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PostPosted: Jan 07, 2021 02:47    Post subject: Re: Pyrite with bubble-like growths  

Mathias wrote:
I thought that pyrite won't melt, upon heating it will decompose to Iron and Sulphur at a certain temperature.


Hi, Mathias. How are you?

You are right!
In the Scarlino plant (a few kilometers from Gavorrano mine), the largest in Europe for the production of sulfuric acid, pyrite was roasted at 750°C to obtain sulfur dioxide.
But I must admit that I don't know what can happen in a natural geological context, with different conditions of temperature, pressure and mineral fluids present.
As I said, my conjecture is "very naive". :-)

Warm greetings from Gavorrano.
Sante
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PostPosted: Jan 07, 2021 02:53    Post subject: Re: Pyrite with bubble-like growths  

Bob Morgan wrote:
Could some of these structures be spiral growth hillocks with rounded edges? Such tend to develop on small cracks or irregular boundaries on the underlying surface.


Hi Bob. I hope you are fine.

I suppose you're referring to Pete's specimen and not to mine.

Warm greetings.
Sante
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PostPosted: Jan 07, 2021 14:48    Post subject: Re: Pyrite with bubble-like growths  

Hi, Sante, all,
The answer is complex.
In industry, sulfuric acid can be prepared by the pyrite roasting process.
In rotary kilns, pyrites are burnt in the presence of air at high temperature. SO2 (sulfur dioxide) is obtained.

After SO2 is oxidized to SO3 (sulfuric oxide), to obtain sulfuric acid with water.

In rocks (ores),
Due to the lack of oxygen, other chemical and biological processes take place (acid runoff in mines).

Attacks by bacteria are also the cause.
This bacterial activity is very old on Earth (origins of marine life near black smokers). It has been discovered on ocean ridges where it appears on manganese nodules.
These bacteria are called:
Ferrobacillus ferrooxidans (Fe2 +)
Acidithiobacillus ferrooxidans (S, Fe2 +) And many others.
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PostPosted: Jan 07, 2021 14:57    Post subject: Re: Pyrite with bubble-like growths  

This thread has produced a lot more comments than I had expected! I feel I should respond briefly to the ones since my last comment. In order in which they were posted:

Philippe: There could be something inside the crystal, as you suggest, but usually the crystal would just grow around it, like water rising over a pebble. It would not be like "a rug over an object" at least in the sense that there would not be atomic layers of pyrite wrapped over the impurity. Had that been the case, our x-ray crystallography studies would have detected it.

Alfredo: Thanks for the comment. I did not mean to imply that this phenomenon would be confined to pyrite or other metallic minerals. I've never seen it on Herkimer diamonds; I'd love to see that some time!

Roger: yours is a complex hypothesis, but I suppose a possible explanation. I do think the "bubbles" are late-stage growths, maybe even in a second separate stage of growth. I find it hard to understand the recurved, concave outer edge of the profile as resulting from dissolution, though.

Mathias: your galena is very interesting! Looks like a slightly depressed cube face with the bumps on it. I would think that if something happened inside to "push them up", the expansion would have caused them to crack. I suspect they grew that way, and are generally similar to my bubbles.

John: Fantastic fluorapatite! To me, the surface ornamentation is suggestive of growth hillocks of the sort that Bob mentioned later, or maybe renewed crystallization at specific points. In that sense the bumps might be comparable to my bubbles, except of course that they are bounded by crystal faces, not continuous "liquid" surfaces.

Dean: I think a concretion-like process would probably produce polycrystalline bumps. Your second idea is similar to mine in that it says "something special happened in specific places to make this happen", which is clearly true! And like mine it does not completely explain what happened (and why it does not happen more often). The faces of the pyrite around the bubble are mirror sharp, which would seem unlikely if they had altered enough to form even a thin coat of hematite or goethite.

Sante: Hi! These crystals occur in an environment that has never been above 100°C, probably not above 60°. There was no melting! The role of crystallographic continuity: it is part of the enigma - a surface feature that apparently is not reflected at all in the underlying structure! As you say, your melnikovite has only an apparent similarity - it is amorphic and not crystallographically related to the pyrite - it could equally well form on a quartz crystal, or directly on a rock matrix.

Mathias: Yes, you are right. Pyrite decomposes to pyrrhotite and sulfur at about 540°C; the sulfur is presumably molten at this temperature. According to one phase diagram I saw, this becomes liquid at about 1080°. This diagram says nothing about pressure, so presumably it is for surface pressures. The phase diagram presumably assumes a closed system, so there would not be any air to "roast" the sulfur, in the manner that Sante writes of.

Bob: Growth hillocks usually form around screw defects. The ones I have seen are generally not as smooth in texture, and they are much flatter than these. The merit of the idea is that it produces a raised structure without disturbing the crystal structure correspondingly. It would not explain the examples where the bubble-like surface occurs between two crystals, looking like a film of water.


This reply contains a lot of statements saying "No, that's not it"! And I think I am correct in saying so. I hope I don't offend anyone; I really appreciate the suggestions, even if I think they are not the answer. I have been puzzling about these little bubbles for 30 years or more (they were collected in the late 1980s) and my best ideas are still not totally satisfying, even to me! Reading and considering all these responses has reminded me of some of the weak spots in my own hypotheses, so I have some work to do! Thanks to all!

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PostPosted: Jan 08, 2021 16:25    Post subject: Re: Pyrite with bubble-like growths  

Hello everybody!
This is probably due to anti skeletal growth. Crystals of a cubic system during anti skeletal growth under ideal conditions grow in the form of a ball.
The area of each subsequent layer decreases as the growth conditions deteriorate. Accordingly, the concave outer edge of the profile is the result of growth changes.
(imho) Roger Warin correctly described gist.



bubble_101.jpg
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bubble_101.jpg


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PostPosted: Jan 09, 2021 09:21    Post subject: Re: Pyrite with bubble-like growths  

Pete,
The 'bubbles' aren't overgrowths. Pyrite is too rigorously isometric to do something like that on the surface of sharp crystals. They have nothing to do with dissolution. The crystals would show dissolution effects.
The 'bubbles' are best explained as prior structures with the sharp crystals as overgrowths, and the 'bubbles' being what of those structures has not been overgrown.
What they were? Who knows? They remind me of goethite or hematite? Can such pseudomorph into pyrite? Perhaps the circular feature is the result of iron removed to contribute to the overgrowing pyrite crystal.
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